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| United States Patent |
5,312,799
|
|
Seckinger
, et al.
|
May 17, 1994
|
Amides
Abstract
This invention described in this patent application relates to novel amides
of the formula (I)
##STR1##
wherein the substituents are as defined in the disclosure, intermediates
for such amides, synthesis thereof and their use for the control of weeds.
| Inventors:
|
Seckinger; Karl (Riegel, DE);
Milzner; Karlheinz (Basel, CH);
Kuhnen; Fred (Weil, DE);
Mohanty; Sasank S. (Baden, CH)
|
| Assignee:
|
Sandoz Ltd. (Basel, CH)
|
| Appl. No.:
|
880424 |
| Filed:
|
May 8, 1992 |
Foreign Application Priority Data
| Current U.S. Class: |
504/249; 504/221; 504/224; 504/287; 544/54; 544/58.4; 546/226; 548/567 |
| Intern'l Class: |
A01N 043/86; A01N 043/40; C07D 211/06; C07D 207/46 |
| Field of Search: |
546/226
504/249,287
548/567
|
References Cited
U.S. Patent Documents
| 5055450 | Oct., 1991 | Edwards et al. | 514/19.
|
| 5194084 | Mar., 1993 | Findeisen et al. | 504/273.
|
| 5211739 | May., 1993 | Lopez | 504/273.
|
| Foreign Patent Documents |
| 881227 | Jul., 1980 | BE.
| |
| 0070389 | Jan., 1983 | EP.
| |
| 0221439 | May., 1987 | EP.
| |
| 0264865 | Apr., 1988 | EP.
| |
| 57-045105 | Mar., 1982 | JP.
| |
| 59-048481 | Jun., 1984 | JP.
| |
| 949729 | Feb., 1964 | GB.
| |
| 1114397 | May., 1968 | GB.
| |
Other References
C.A. 92.141802 (1980).
C.A. 87.118063x(1977).
|
Primary Examiner: Shah; Mukund J.
Assistant Examiner: Grumbling; Matthew V.
Attorney, Agent or Firm: Norris; Allen E.
Claims
What is claimed is:
1. A compound of the formula (I)
##STR14##
wherein R is H, C.sub.1-3 alkyl or C.sub.2-3 alkenyl optionally
substituted by halo; or is C.sub.2-3 alkinyl;
R.sub.1 is phenyl(C.sub.1-4 alkyl).sub.n, wherein the phenyl group is
optionally substituted by one or more groups selected from
--C(O)--O--C.sub.1-4 alkyl, C.sub.1-8 alkyl, C.sub.1-8 haloalkyl, halo,
nitro, cyano, --SO.sub.2 C.sub.1-4 alkyl, SO.sub.2 NR.sub.5 R.sub.5 ' and
S(O)NR.sub.5 R.sub.5 '; or is C.sub.5-8 cycloalkenyl; --N.dbd.R.sub.6 ;
C.sub.2-8 alkenyl, C.sub.1-8 alkyl or C.sub.3-5 alkinyl optionally
substituted with one or more halo; or is C.sub.1-4 alkyl--SO.sub.2
--C.sub.1-4 alkyl;
R.sub.2 is halo or hydrogen;
R.sub.3 is halo, cyano or C.sub.1-4 alkyl;
R.sub.4 is H; NO.sub.2 ; NH.sub.2 ; CN; C.sub.1-8 alkyl optionally
substituted by CN; C.sub.2-8 alkenyl optionally substituted by CN;
C.sub.2-5 alkinyl; (C.sub.2-5 alkoxycarbonyl)-C.sub.1-4 alkyl, whereby the
carbon atom of the alkyl group alpha to the alkoxycarbonyl group may bear
one more C.sub.2-5 alkoxcarbonyl groups or a cyano group; (C.sub.2-5
alkoxycarbonyl)-C.sub.-4 alkoxy-C.sub.1-4 alkyl; (C.sub.2-5
alkoxycarbonyl)-C.sub.1-4 alkylamino-C.sub.1-4 alkyl; (C.sub.2-5
alkoxycarbonyl)-C.sub.2-5 alkenyl, whereby the alkenyl moiety is
optionally substituted by halogen; C.sub.1-4 alkylthio-C.sub.1-4 alkyl;
C.sub.1-4 alkylsulfonyl-C.sub.1-4 alkyl; C.sub.1-4 alkoxy-C.sub.1-4
alkoxy; X(Alk).sub.m R.sub.7 ; OCH(SR.sub.8)-COOR.sub.9 ; NR.sub.10
R.sub.11 ; COOR.sub.12 ; CONR.sub.13 R.sub.13 '; COR.sub.14 or R.sub.15 ;
or R.sub.3 and R.sub.4 join together with the phenyl ring to form a
bicyclic ring containing nine to ten ring atoms, one to three of said ring
atoms optionally being selected from oxygen, nitrogen and sulfur, and
optionally being substituted with one or more groups selected from
C.sub.3-8 alkinyl, C.sub.1-8 alkyl, halo, oxo, C.sub.1-4
alkylene-R.sub.16, and C.sub.2-8 alkenyl;
R.sub.5 and R.sub.5, independently are C.sub.1-4 alkyl;
R.sub.6 is C.sub.2-8 alkylidene;
R.sub.7 is H; C.sub.1-4 alkyl, C.sub.2-5 alkenyl C.sub.2-5 alkinyl, or
C.sub.3-8 cycloalkyl, which hydrocarbyl is unsubstituted or substituted by
one or more halogen or by CN; cyclopentanonyl; phenyl optionally
substituted by O--Alk'--COOR.sub.8 ; or is C.sub.2-5 alkanoyl; C.sub.2-5
alkoxycarbonyl; C.sub.2-8 (alkoxycarbonyl)(C.sub.3-8
cycloalkyloxy)-carbonyl, in which the alkoxy or cycloalkyloxy group is
optionally substituted by one or more halo; CONR.sub.9 R.sub.8',
C(.dbd.NOR.sub.8)-COOR.sub.8', CN; P(O)(OR.sub.8)(OR.sub.8') or R.sub.15 ;
R.sub.8 and R.sub.8, independently are C.sub.1-4 alkyl;
R.sub.9 is C.sub.1-4 alkyl optionally substituted by one or more halo;
R.sub.10 is H or C.sub.1-4 alkyl;
R.sub.11 is H; C.sub.1-4 alkyl, optionally substituted by
P(O)(OR.sub.8)(R.sub.8'); C.sub.2-5 alkanoyl; C.sub.2-5 alkoxycarbonyl; or
C.sub.2-5 alkoxycarbonyl-C.sub.1-4 alkyl;
R.sub.12 is N.dbd.(C.sub.2-8 alkylidene); C.sub.1-4 alkyl optionally
substituted by one or more groups selected from halo, C.sub.1-4 alkoxy,
tri-C.sub.1-4 alkylsilyloxy, tri-C.sub.1-4 alkyl-silyl, (tri-C.sub.1-4
alkylsilyloxy)-carbonyl, C.sub.2-5 alkoxycarbonyl,
P(O)(OR.sub.8)(OR.sub.8'), C.sub.2-5 alkanoyl-oxy or by di(C.sub.1-4
alkylamino)-carbonyloxy in which both alkyl groups may be tied together to
form a saturated 5 to 6 membered heteroring optionally containing one
further heteroatom selected from O, S and N, and in which any further
N-heteroatom present may, depending on the hydrogenation degree of the
heteroring, bear a hydrogen or a C.sub.1-4 alkyl group;
R.sub.13 is H or C.sub.1-4 alkyl;
R.sub.13, is H, C.sub.1-4 alkyl optionally substituted by halo, C.sub.1-4
alkoxy, phenyl, CHO, C.sub.2-5 alkanoyl, C.sub.1-4 alkylsulfonyl,
(C.sub.2-5 alkoxycarbonyl)-C.sub.1-4 alkyl or(C.sub.2-5
alkoxycarbonyl)-C.sub.1-4 alkoxy;
or R.sub.13 and R.sub.13, together form a 4 to 6 membered heteroring
optionally containing one or two further heteroatoms selected from O, S
and N, whereby, depending on the hydrogenation degree of the heteroring,
any further N-heteroatom may bear hydrogen or be substituted by C.sub.1-4
alkyl;
R.sub.14 is H or C.sub.1-4 alkyl;
R.sub.15 is a heterocyclic ring having 5 or 6 ring atoms, one to three of
said ring atom being selected from oxygen, sulfur and nitrogen, which ring
is optionally substituted with one or more C.sub.1-4 alkyl groups;
R.sub.16 is CN; COOR.sub.12 ; OC.sub.1-4 alkyl; or is 4-tetrahydropyranyl,
2H-5,6-dihydro-thiin-3-yl, 2-pyridyl, 2-pyrazinyl, 1,2-oxazol-3-yl, or
1,2,4-oxdiazol-3-yl, each of which is optionally substituted with
C.sub.1-4 alkyl;
Alk and Alk' independently are C.sub.1-4 alkylene;
n and m independently are 0 or 1;
A is a C.sub.3-4 alkylene or straight chain substituted by one to three
halogen; and
X, Y and Z are independently selected from O and S.
2. A compound of formula (I) according to claim 1 wherein X, Y and Z are
oxygen and R is H.
3. A compound of formula (I) according to claim 1 wherein A is straight
chain butylene substituted by fluorine.
4. A compound of formula (I) according to claim 2 wherein R.sub.2 is
chlorine or fluorine and R.sub.3 is CN, Br, Cl or methyl.
5. A compound of formula (I) according to claim 3 wherein R.sub.2 is
chlorine or fluorine and R.sub.3 is CN, Br, Cl or methyl.
6. A compound of formula (I) according to claim 4 wherein R.sub.1 is
selected from the group consisting of phenyl optionally substituted with
halogen, nitro or CH.sub.3 OC(O)--; C.sub.1-4 alkyl optionally substituted
with one to four halogen atoms; C.sub.2-4 alkenyl; and C.sub.2-3
alkylidene.dbd.N--.
7. A compound of formula (I) according to claim 5 wherein R.sub.1 is
selected from the group consisting of phenyl optionally substituted with
halogen, nitro or CH.sub.3 OC(O)--; C.sub.1-4 alkyl optionally substituted
with one to four halogen atoms; C.sub.2-4 alkenyl; and C.sub.2-3
alkylidene.dbd.N--.
8. A compound of formula (I) according to claim 6 wherein R.sub.4 is
O(Alk).sub.m R.sub.7, COOR.sub.12 or CONR.sub.13 R.sub.13', R.sub.7 is
C.sub.1-4 alkyl, C.sub.2-5 alkenyl, C.sub.2-5 alkinyl or C.sub.2-5
alkoxycarbonyl, R.sub.12 is C.sub.1-4 alkyl optionally substituted by
halo, R.sub.13 is H and R.sub.13, is C.sub.1-4 alkyl optionally
substituted by halo.
9. A compound of formula (I) according to claim 7 wherein R.sub.4 is
O(Alk).sub.m R.sub.7, COOR.sub.12 or CONR.sub.13 R.sub.13', R.sub.7 is
C.sub.1-4 alkyl, C.sub.2-5 alkenyl, C.sub.2-5 alkinyl or C.sub.2-5
alkoxycarbonyl, R.sub.12 is C.sub.1-4 alkyl optionally substituted by
halo, R.sub.13 is H and R.sub.13, is C.sub.1-4 alkyl optionally
substituted by halo.
10. A herbicidal composition comprising a compound of formula (I) as
defined in claim 1 and an agriculturally acceptable carrier.
11. A compound of the formula (II)
##STR15##
wherein R--R.sub.4, A and Z are as defined in claim 1.
12. A method of combatting weeds which comprises applying to the weeds or
their locus a herbicidally effective amount of the compound defined in
claim 1.
Description
This invention relates to novel amides, intermediates therefore, synthesis
thereof, and the use of said compounds for the control of More
particularly, one aspect of this invention relates to a compound of the
formula (I)
##STR2##
wherein
R is H, C.sub.1-3 alkyl or C.sub.2-3 alkenyl optionally substituted by
halo; or is C.sub.2-3 alkinyl;
R.sub.1 is phenyl(C.sub.1-4 alkyl).sub.n, wherein the phenyl group is
optionally substituted by one or more groups selected from
--C(O)--O--C.sub.1-4 alkyl, C.sub.1-8 alkyl, C.sub.1-8 haloalkyl, halo,
nitro, cyano, --SO.sub.2 C.sub.1-4 alkyl, SO.sub.2 NR.sub.5 R.sub.5 ' and
S(O)NR.sub.5 R.sub.5 '; or is C.sub.5-8 cycloalkenyl; --N.dbd.R.sub.6 ;
C.sub.2-8 alkenyl, C.sub.1-8 alkyl or C.sub.3-5 alkinyl optionally
substituted with one or more halo; or is C.sub.1-4 alkyl--SO.sub.2
--C.sub.1-4 alkyl;
R.sub.2 is halo or hydrogen;
R.sub.3 is halo, cyano or C.sub.1-4 alkyl;
R.sub.4 is H; NO.sub.2 ; NH.sub.2 ; CN; C.sub.1-8 alkyl optionally
substituted by CN; C.sub.2-8 alkenyl optionally substituted by CN;
C.sub.2-5 alkinyl; (C.sub.2-5 alkoxycarbonyl)-C.sub.1-4 alkyl, whereby the
carbon atom of the alkyl group alpha to the alkoxycarbonyl group may bear
one more C.sub.2-5 alkoxcarbonyl groups or a cyano group; (C.sub.2-5
alkoxycarbonyl)-C.sub.-4 alkoxy-C.sub.1-4 alkyl; (C.sub.2-5
alkoxycarbonyl)-C.sub.1-4 alkylamino-C.sub.1-4 alkyl; (C.sub.2-5
alkoxycarbonyl)-C.sub.2-5 alkenyl, whereby the alkenyl moiety is
optionally substituted by halogen; C.sub.1-4 alkylthio-C.sub.1-4 alkyl;
C.sub.1-4 alkylsulfonyl-C.sub.1-4 alkyl; C.sub.1-4 alkoxy-C.sub.1-4
alkoxy; X(Alk).sub.m R.sub.7 ; OCH(SR.sub.8)-COOR.sub.9 ; NR.sub.10
R.sub.11 ; COOR.sub.12 ; CONR.sub.13 R.sub.13 '; COR.sub.14 or R.sub.15 ;
or R.sub.3 and R.sub.4 join together with the phenyl ring to form a
bicyclic ring containing nine to ten ring atoms, one to three of said ring
atoms optionally being selected from oxygen, nitrogen and sulfur, and
optionally being substituted with one or more groups selected from
C.sub.3-8 alkinyl, C.sub.1-8 alkyl, halo, oxo, C.sub.1-4
alkylene-R.sub.16, and C.sub.2-8 alkenyl;
R.sub.5 and R.sub.5 ' independently are C.sub.1-4 alkyl;
R.sub.6 is C.sub.2-8 alkylidene;
R.sub.7 is H; C.sub.1-4 alkyl, C.sub.2-5 alkenyl C.sub.2-5 alkinyl, or
C.sub.3-8 cycloalkyl, which hydrocarbyl is unsubstituted or substituted by
one or more halogen or by CN; cyclopentanonyl; phenyl optionally
substituted by O--Alk'--COOR.sub.8 ; or is C.sub.2-5 alkanoyl; C.sub.2-5
alkoxycarbonyl; C.sub.2-8 (alkoxycarbonyl)(C.sub.3-8
cycloalkyloxy)carbonyl, in which the alkoxy or cycloalkyloxy group is
optionally substituted by one or more halo; CONR.sub.9 R.sub.8 ',
C(.dbd.NOR.sub.8)--COOR.sub.8 ', CN; P(O)(OR.sub.8)(OR.sub.8 ') or
R.sub.15 ;
R.sub.8 and R.sub.8 ', independently are C.sub.1-4 alkyl;
R.sub.9 is C.sub.1-4 alkyl optionally substituted by one or more halo;
R.sub.10 is H or C.sub.1-4 alkyl;
R.sub.11 is H; C.sub.1-4 alkyl, optionally substituted by
P(O)(OR.sub.8)(R.sub.8 '); C.sub.2-5 alkanoyl; C.sub.2-5 alkoxycarbonyl;
or C.sub.2-5 alkoxycarbonyl-C.sub.1-4 alkyl;
R.sub.12 is N.dbd.(C.sub.2-8 alkylidene); C.sub.1-4 alkyl optionally
substituted by one or more groups selected from halo, C.sub.1-4 alkoxy,
tri-C.sub.1-4 alkylsilyloxy, tri-C.sub.1-4 alkyl-silyl, (tri-C.sub.1-4
alkylsilyloxy)-carbonyl, C.sub.2-5 alkoxycarbonyl, P(O)(OR.sub.8)(OR.sub.8
'), C.sub.2-5 alkanoyl-oxy or by di(C.sub.1-4 alkylamino)-carbonyloxy in
which both alkyl groups may be tied together to form a saturated 5 to 6
membered heteroring optionally containing one further heteroatom selected
from O, S and N, and in which any further N-heteroatom present may,
depending on the hydrogenation degree of the heteroring, bear a hydrogen
or a C.sub.1-4 alkyl group;
R.sub.13 is H or C.sub.1-4 alkyl;
R.sub.13 ' is H, C.sub.1-4 alkyl optionally substituted by halo, C.sub.1-4
alkoxy, phenyl, CHO, C.sub.2-5 alkanoyl, C.sub.1-4 alkylsulfonyl,
(C.sub.2-5 alkoxycarbonyl)-C.sub.1-4 alkyl or(C.sub.2-5
alkoxycarbonyl)-C.sub.1-4 alkoxy;
or R.sub.13 and R.sub.13 ' together form a 4 to 6 membered heteroring
optionally containing one or two further heteroatoms selected from O, S
and N, whereby, depending on the hydrogenation degree of the heteroring,
any further N-heteroatom may bear hydrogen or be substituted by C.sub.1-4
alkyl;
R.sub.14 is H or C.sub.1-4 alkyl;
R.sub.15 is a heterocyclic ring having 5 or 6 ring atoms, one to three of
said ring atom being selected from oxygen, sulfur and nitrogen, which ring
is optionally substituted with one or more C.sub.1-4 alkyl groups;
R.sub.16 is CN; COOR.sub.12 ; OC.sub.1-4 alkyl; or is 4-tetrahydropyranyl,
2H-5,6-dihydro-thiin-3-yl, 2-pyridyl, 2-pyrazinyl, 1,2-oxazol-3-yl, or
1,2,4-oxdiazol-3-yl, each of which is optionally substituted with
C.sub.1-4 alkyl;
Alk and Alk' independently are C.sub.1-4 alkylene;
n and m independently are 0 or 1;
A is a C.sub.3-4 alkylene or C.sub.3-4 alkenylene straight chain optionally
substituted by one to three halogen; or is a propylene or propenylene
straight chain interposed by a heteroatom or heterogroup selected from S,
O, SO, SO.sub.2, and NR.sub.10 ; and
X, Y and Z are independently selected from O and S.
Where R.sub.1 is or contains a C.sub.1-8 alkyl group or R.sub.4 is a
C.sub.1-8 alkyl group, it is preferably a C.sub.1-4 alkyl group. Any alkyl
group may be branched or straight chain.
Where R.sub.1 is a C.sub.2-8 alkenyl group, it is preferably a C.sub.2-5
alkenyl group. Any alkenyl group may be either branched or straight chain.
Where the bicyclic ring formed by junction of R.sub.3 and R.sub.4 is
substituted by a C.sub.3-8 alkinyl group, it is preferably a C.sub.3-5
alkinyl group. Any alkinyl groups may be either branched or straight
chain.
Where R.sub.1 is a C.sub.5-8 cycloalkenyl group, it is preferably a
C.sub.5-6 cycloalkenyl group.
Where R.sub.7 contains a C.sub.3-8 CYcloalkyl group, it is preferably a
C.sub.3-5 cycloalkyl group.
Where R.sub.1, R.sub.4, R.sub.7 or R.sub.2 contains halogen, it is
preferably chlorine or fluorine.
R.sub.6 may be straight or branched chain; it may be cyclic or contain a
cycloalkyl group.
Where R.sub.6 cycloalkylidene, it is preferably C.sub.3-6 cycloalkylidine,
more preferably C.sub.2-6 cycloalkylidene.
Where R.sub.6 is branched or straight chain alkylidene it is preferably
C.sub.2-8 alkylidene, more preferably C.sub.2-5 alkylidene.
Where R.sub.3 and R.sub.4 join together with the phenyl ring to form a
bicyclic ring, it is preferably an indanone; a benzazinone, particularly a
quinolinone; a benzoxazinone; a benzodiazinone particularly
dihydroquinoxalinone; a benzothiazinone; a benzodioxane; a benzopyrane; a
benzopyrone, particularly coumarin; a benzazole, particularly an indole,
an indolone, an indazole, a benzotriazole, an isatine or a
benzimidazolone; a benzoxazolone; a benzothiazolone; a benzofurane; or a
benzdioxolane;
Where R.sub.1, R.sub.4, R.sub.7, R.sub.9, R.sub.12, R.sub.15 or A are
substituted, they are preferably mono-, di- or tri-substituted.
X, Y and Z are preferably oxygen.
R is preferably H.
R.sub.1 is preferably selected from phenyl optionally substituted with
halogen, nitro or CH.sub.3 OC(O)--; C.sub.1-4 alkyl optionally substituted
with one to four halogen atoms; C.sub.2-4 alkenyl; or C.sub.2-3
alkylidene.dbd.N--.
R.sub.2 is preferably chlorine or fluorine, more preferably fluorine.
R.sub.3 is preferably CN, Br, Cl or methyl.
R.sub.4 is preferably O(Alk).sub.m R.sub.7, COOR.sub.12 or CONR.sub.13
R.sub.3 ';
R.sub.7 is preferably C.sub.1-4 alkyl, C.sub.2-5 alkenyl, C.sub.2-5
alkinyl, or C.sub.2-5 alkoxycarbonyl.
R.sub.12 is preferably C.sub.1-4 alkyl optionally substituted by halo.
R.sub.13 is preferably H.
R.sub.13 ' is preferably C.sub.1-4 alkyl optionally substituted by halo.
R.sub.15 is preferably an azole particularly pyrazol, triazol or
benzimidazol; thiophene; furane; oxadiazole; oxazoline; dioxolane;
dithiolane; pyrane; or dihydro- or tetrahydrothiine; and is preferably a
heteroring containing 1-3 heteroatoms.
A is preferably straight chain butylene substituted by fluorine.
Alk is preferably CH.sub.2 or CH(CH.sub.3);
Compounds of the formula (I) may be prepared by reacting a compound of the
formula (II)
##STR3##
with a compound of the formula (III)
##STR4##
wherein R--R.sub.4, A, X, Y and Z are as previously defined and W.sub.1 is
halogen.
This reaction is suitably carried out at 0.degree.-50.degree. C. in an
inert solvent such as methylene chloride, chloroform, acetone,
acetonitrile or ether in the presence of a base such as triethylamine,
sodium carbonate or potassium carbonate. The compound of the formula (I)
may be recovered from solution by standard techniques, such as
liquid-liquid phase separation, and subsequent evaporation in vacuo.
Compounds of the formula (II) are believed to be novel, and form another
aspect of this invention.
Compounds of the formula (II) can be prepared by reacting a compound of the
formula (IV)
##STR5##
with a compound of the formula (V)
##STR6##
wherein A, Z, R and R.sub.2-4 are as previoiusly defined and W.sub.2 is
halogen.
This reaction is exothermic and is suitably carried out at
0.degree.-500.degree. C. in an inert solvent as previously mentioned.
After the reaction subsides, a suitable base, as previously mentioned, is
added, after which the reaction mixture is stirred. The compound of the
formula (II) may be recovered from solution by standard techniques, such
as liquid-liquid phase separation, and subsequent evaporation in vacuo.
Compounds of the formulae (III), (IV) and (V) are known, or can be prepared
according standard techniques from known compounds.
The compounds of formula (I) are useful because they control the growth of
plants. By plants it is meant germinating seeds, merging seedlings and
established vegetation including underground portions. In particular, the
compounds are useful as herbicides as indicated by causing damage to both
monocotyledoneous and dicotyledoneous plants in various standard
evaluations for determining such effects. The herbicidal effects are
exhibited both pre- and post-emergence the plants. Such herbicidal effects
indicate that the compounds of formula (I) are particularly of interest in
combatting weeds (unwanted plants).
The compounds of the formula (I) are indicated mainly to be stronger acting
against dicotyledoneous plants than monocotyledoneous plants. Relatively
less toxicity towards crops than towards weeds is further indicated.
Hence, the compounds are of particular interest as selective herbicides to
combat weeds in a crop locus, particularly as locus of a crop such as, for
example, sugarbeet, sunflower, cotton soybean, corn and wheat.
The present invention therefore also provides a method of combatting weeds
in a locus which comprises applying to the weeds or their locus a
herbicidally effective amount of a compound of the invention. When
selective action is desired in crop locus, the amount applied will be
sufficient to combat weeds without substantially damaging the crop.
For general herbicidal as well as selective herbicidal use of the compounds
of the invention, the particular amounts to be applied will vary depending
upon recognized factors such as the compound employed, the plants
primarily in the locus, the timing, mode and formulation in application,
the various conditions of treatment such as soil and weather and the like.
However, in general, satisfactory results in weed control are usually
obtained upon application of the compounds of the invention at a rate in
the range of from 0.01 to 10 kg/hectare, more usually 0.05 to 2
kg/hectare, and preferably 0.1 to 1 kg/hectare, the application being
repeated as necessary. When used in crops, the application usually will
not exceed about 5 kg/hectare, and is usually in the range of 0.01 to 1
kg/hectare.
For practical use as herbicides, the compounds of formula (I) may be and
are preferably employed in herbicidal compositions comprising a herbicidal
effective amount of the compound and an inert carier which is
agriculturally acceptable in the sense of not, by reason of its presence,
poisoning the agricultural environment including the immediate soil of
application or any crops present therein or otherwise being unsafe for
application. Such compositions of formulations may contain 0.01% to 99% by
weight of active ingredient, from 0 to 20% by weight of agriculturally
acceptable surfactants and 1 to 99.99% by weight of the inert carrier.
Higher ratios of surfactant to active ingredient are sometimes desirable
and are achieved by incorporation into the formulation or by tank mixing.
Application forms of composition typically contain between 0.01 and 25% by
weight of active ingredient, but lower or higher levels of active
ingredient can, of course, be present depending on the intended use and
the physical properties of the compound. Concentrate forms of composition
intended to be diluted before use generally contain between 2 and 90%,
preferably between 10 and 80% by weight of active ingredient.
Useful compositions or formulations of the compounds of the invention
include dusts, granules, pellets, suspension concentrates, wettable
powders, emulsifiable concentrates and the like. They are obtained by
conventional manner, e.g. by mixing the compounds of the invention with
the inert carrier. More specifically, liquid compositions are obtained by
mixing the ingredients, fine solid compositions by blending and, usually
grinding, suspensions by wet milling and granules and pellets by
impregnating or coating (preformed) granular carriers with the active
ingredient or by agglomeration techniques.
For example, dusts can be prepared by grinding and blending the active
compound with a solid inert carrier such as talc, clay, silica and the
like. Granular formulations can be prepared by impregnating the compound,
usually dissolved in a suitable solvent, onto and into granulated carriers
such as the attapulgites or the vermiculites, usually of a particle size
range of from about 0.3 to 1.5 mm. Wettable powders, which can be
dispersed in water or oil to any desired concentration of the active
compound, can be prepared by incorporating wetting agents into
concentrated dust compositions.
Alternatively, the compounds of the invention may be used in
micro-encapsulated form.
Agriculturally acceptable additives may be employed in the herbicidal
compositions to improve the performance of the active ingredient and to
reduce foaming, caking and corrosion. Surfactant as used herein means
agriculturally acceptable material which imparts emulsifiability,
spreading, wetting, dispersiblity or other surface-modifying properties
properties. Examples of surfactants are sodium lignin sulphonate and
lauryl sulphate.
Carriers as used herein mean a liquid or solid material used to dilute a
concentrated material to a usable or desirable strength. For dusts or
granules it can be e.g. talc, kaolin or diatomaeous earth, for liquid
concentrate forms, a hydrocarbon such as xylene or an alcohol such as
isopropanol; and for liquid application forms, e.g. water or diesel oil.
The compositions of this application can also comprise other compounds
having biological activity, e.g. compounds having similar or complementary
herbicidal ativity or compounds having antidotal, fungicidal or
insecticidal activity.
Typical herbicidal composition, according to this invention, are
illustrated by the following Examples A, B and C in which the quantities
are in parts by weight.
EXAMPLE A
Preparation of a Dust
10 Parts of a compound of formula (I) and 90 parts of powdered talc are
mixed in a mechanical grinder-blender and are ground until a homogeneous,
free-flowing dust of the desired particle size is obtained. This dust is
suitable for direct application to the site of the weed infestation.
EXAMPLE B
Preparation of Wettable Powder
25 Parts of a compound of formula (I) are mixed and milled with 25 parts of
synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts of
sodium ligninsulphonate and 45 parts of finely divided kaolin until the
mean particle size is about 5 micron. The resulting wettable powder is
diluted with water before use to a spray liquor with the desired
concentration.
EXAMPLE C
Preparation of Emulsifiable Concentrate (EC)
13.37 Parts of a compound are mixed in a beaker with 1.43 parts of Toximul
360A (a mixture of anionic and non-ionic surfactants containing largely
anionic surfctants), 5.61 parts of Toximul 360A (a mixture of anionic and
non-ionic surfactants containing largely non-ionic surfactants), 23.79
parts of dimethylformamide and 55.8 parts of Tenneco 500-100
(predominantly a mixture of alkylated aromatics such as xylene and
ethylbenzene) until solution is effected. The resulting EC is diluted with
water for use.
FINAL COMPOUNDS
EXAMPLE 1--1
2[[(4-chloro-2-fluoro-5-isopropoxyphenyl)amino]carbonyl]-1-piperidine
carboxylic acid-phenylester
To 15.6 g (0.05 mol) pipecolic acid 4-chloro-2-fluoro 5-isopropoxy anilide
dissolved in 250 ml methylenchloride are added 5.5 g (0.054 mol)
triethylamine. 7.8 g (0.05 mol) of phenylchloroformate are added dropwise
and the reaction mixture is stirred for 15 minutes at room temperature.
100 ml water is added and the organic layer is separated, washed with
additional 100 ml water, dried (MgSO.sub.4) and evaporated in vacuo. The
residue is homogenous by TLC (Rf.dbd.0.76 CH.sub.2 --CH.sub.2 /CH.sub.3
OH, 98:2)
In an analogous manner, the following compounds of formula (Ia) set forth
in Table 1 are made.
TABLE 1
______________________________________
##STR7## (Ia)
______________________________________
For compounds 1-2 through 1-184 and 221 through 227 Ar is 2-R.sub.2
-4-R.sub.3 05-R.sub.4 -phenyl.
For compounds 1-185 through 1-220, Ar is as indicated.
The orientation of the alkylene or alkenylene chain "A" set forth below is
such that the first carbon in the chain is bound to the nitrogen in
formula (Ia).
Compd. R.sub.1 A X Y Z R.sub.2 R.sub.3 R.sub.4 mp .degree.C. or R.sub.f
(silica gel)
1-2 phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2 CCH 130.degree. C.
1-3 " " " " " " " H 82.degree. C. 1-4 " " " " " " " OCH.sub.3 R.sub.f =
0,25 (CH.sub.2 CH.sub.2) 1-5 " " " " " " " OCH.sub.2 CH.sub.3 R.sub.f =
0,67(CH.sub.2 Cl.sub.2 /CH.sub.3
OH, 98:2) 1-6 " " " " " " " OCOOCH.sub.3 R.sub.f = 0,75 (Acetone) 1-7 "
" " " " " " OCH.sub.2CH.sub.2CH.sub.3 Rf = 0,65 (CH.sub.2 CH.sub.2
/CH.sub.3 OH, 98:2) 1-8 CH.sub.3 CH.sub.2 " " " " " " H 67.degree. C.
1-9 " " " " " " " OCH.sub.3 R.sub.f = 0,13 (CH.sub.2 Cl.sub.2) 1-10 " "
" " " " " OCH(CH.sub.3).sub.2 R.sub.f = 0,55 (CH.sub.2 Cl.sub.2
/CH.sub.3 OH, 98:2) 1-11 benzyl " " " " " " OCH.sub.3 R.sub.f = 0,35
(CH.sub.2 Cl.sub.2) 1-12 " " " " " " " OCH(CH.sub.3).sub.2 118.degree.
C. 1-13 CH.sub.3 " " " " " " " 92.degree. C. 1-14 " CHCHSCH.sub.2 " " "
" " " 1-15 CH.sub.3 OCO-phenyl " " " " " " " R.sub.f = 0,54 (CH.sub.2
Cl.sub.2 /CH.sub.3 OH, 98:2) 1-16 CH.sub.3 OCO-phenyl " " " " " "
OCH.sub.2 CH.sub.2 CH.sub.3 R.sub.f = 0,59 (CH.sub.2 Cl.sub.2 /CH.sub.3
OH, 98:2) 1-17 CH.sub.3 OCO-phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2
CH.sub.3 R.sub.f = 0,56 (CH.sub.2 Cl.sub.2 /CH.sub.3 OH, 98:2) 1-18
phenyl " S " " " " OH(CH.sub.3).sub.2 103.degree. C. 1-19 " " " " " " "
OCH.sub.2 CH.sub.2 CH.sub.3 105.degree. C. 1-20 4-CH.sub.3 -phenyl " " "
" " " OCH(CH.sub.3).sub.2 100.degree. C. 1-21 " " " " " " " OCH.sub.2
CH.sub.2 CH.sub.3 R.sub.f = 0,72 (CH.sub.2 Cl.sub.2 /CH.sub.3 OH, 98:2)
1-22 4-Cl-phenyl " " " " " " OCH(CH.sub.3).sub.2 135.degree. C. 1-23 " "
O S " " " OCH(CH.sub.3).sub.2 R.sub.f = 0,64 (CH.sub.2 CH.sub.2
/CH.sub.3 OH, 98:2) 1-24 " " " O " " " " R.sub.f = 0,60 (CH.sub.2
Cl.sub.2 /CH.sub.3 OH, 98:2) 1-25 CH.sub.2CHCH.sub.2 " " " " " " "
R.sub.f = 0,69 (Acetone) 1-26 (CH.sub.3).sub.2 CHCHCl " " " "" " "
R.sub.f = 0,18 (CH.sub.2 Cl.sub.2) 1-27 Cl.sub.3 CCHCl " " " " " " "
55.degree. C. 1-28 CH.sub.2CH " " " " " " " 92.degree.
C. 1-29 (CH.sub.3).sub.2 CN " " " " " " " 56.degree.
C. 1-30 (CH.sub.3).sub.2 CN (CH.sub.2).sub.4 O O O F Cl OC.sub.5
H.sub.9 -cycl. 154.degree. 1-31 phenyl " " " " " " NH.sub.2 R.sub.f =
0,42 (ethyl acetate, hereinafter Est/Hex, 1:1) 1-32 " " " " " "
F F 52.degree. C. 1-33 "" " " " " Cl I 93.degree. C. 1-34 " " " " " " "
OCCH.sub.3 R.sub.f =
0,45 (Est/Hex, 1:1) 1-35 " (CH.sub.2).sub.2SCH.sub.2 " " " " " OCH(CH.su
b.3).sub.2 105-105.degree.; R.sub.f = 0,54 (Et.sub.2 O) 1-36 CH.sub.3 "
" " " " " " 83-84.degree.; R.sub.f = 0,44 (Et.sub.2 O) 1-37 " " " " " "
" OCH(CH.sub.3) CH R.sub.f = 0.38 (Est-Hex 1:1) 1-38 (CH.sub.3).sub.2 CN (
CH.sub.2).sub.4 " " " " " OC.sub.4 H.sub.9 -sec 127.degree. 1-39
4-Cl-phenyl CH.sub.2
CHCHCH.sub.2 " " " "" OCH(CH.sub.3).sub.2 93-95.degree. 1-40 4-NO.sub.2
-phenyl (CH.sub.2).sub.3 " " " " " OC.sub.2 CCH 142.degree.C. 1-41
4-Cl-phenyl " " " " " " " 144.degree. C. 1-42 phenyl " " " " " " "
132.degree. C. 1-43 " " " " " " " OCOOCH.sub.3 63.degree. C. 1-44 "
(CH.sub.2).sub.2SCH.sub.2 " " " " " OCH.sub.3 121.degree. 1-45 " " " " "
" " OC.sub.2 H.sub.5 R.sub.f = 0,49 (Est/Hex 1:1) 1-46 " " " " " " "
OC.sub.3 H.sub.7 -n R.sub.f = 0,51 (Est/Hex 1:1) 1-47 4-Cl-phenyl
(CH.sub.2).sub.2 CH(F)(CH.sub.2) O O O F Cl OCHCH.sub.3CCH 1-48 " " " "
" " " OCH(CH.sub.3).sub.2 1-49 " (CH.sub.2).sub.4 " " " " " OCH.sub.2
-phenyl 1-50 " " " " " " " OCH(CH.sub.3)phenyl 1-51 " " " " " " "
OCHCH.sub.3CH.sub.2 OCH.sub.3 1-52 " " " " " " " OCH.sub.2 COCH.sub.3
1-53 " " " " " " " OCH.sub.2 CHCH.sub.2 1-54 " " " " " " " OCH.sub.2
CHCHCl 1-55 " " " " " " " OCH.sub.2 CClCH.sub.2 1-56 " " " " " " "
OCH.sub.2 -(2,2-di-Cl- cyclopropyl) 1-57 " " " " " " " OCH.sub.2
-(2-Cl-cyclopropyl) 1-58 " " " " " " " OCH.sub.2 -cyclopropyl 1-59
phenyl (CH.sub.2).sub.2SCH.sub.2 " " " " " OC.sub.4 H.sub.9 -sec R.sub.f
= 0,56 (Est/Hex 1:1) 1-60 " " " " " " " OC.sub.4 H.sub.9 -cycl
134-135.degree. 1-61 " " " " " " " OCH.sub.2 CCH 131-132.degree. 1-62 "
" " " " " " OCH(CH.sub.3)CCH R.sub.f -0,27 (Est/Hex 1:3)
1-634-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl OCH.sub.2 CH.sub.2 OCH.sub.2
CH.sub.3 1-64 " " " " " " " OCH.sub.2 -(2-tetrahydrofuryl) 1-65 " " " "
" " " OCH.sub.2 -(2-tetrahydropyranyl) 1-66 " " " " " " " OCH.sub.2
-(2H-5,6-dihydrothiin-3-yl) 1-67 " " " " " " " OCHCH.sub.3COOEt 1-68 " "
" " " " " OCH.sub.2
CN 1-69 " " " " " " " OCH.sub.2C(NOCH.sub.3)COOC.sub.2 H.sub.5 1-70 " "
" " " " " OCH.sub.2 -(1,3-dioxolan-2-yl) 1-71 " " " " " " " OCH.sub.2
-(1,3-dithiolan-2-yl) 1-72 " " " " " " " OCH.sub.2CO-(1,4-oxazin-4-yl)
1-73 " (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " " OCH.sub.2 COOC.sub.5
H.sub.11 -n 1-74 " (CH.sub.2).sub.4 " " " " " O-(-2-oxo-cyclopentyl)
1-75 " " " " " " " OPO(OCH.sub.3).sub.2 1-76 CH.sub.2CHCH.sub.3 (CH.sub.2
).sub.2 CH(F)CH.sub.2 " " " " " OCH(CH.sub.3)CCH 1-77 " (CH.sub.2).sub.4
" " " " " OCH.sub.2 CHCH.sub.2 1-78 " " " " " " " OCHCH.sub.3COOCH.sub.2
CH.sub.3 1-79 4-Cl-phenyl " " " " " " OCH(SCH.sub.3)COOCH.sub.2 CH.sub.2
Cl
1-80 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl
##STR8##
1-81 phenyl (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " " OCH.sub.2
CF.sub.3 1-82 " " " " " " " OCHF.sub.2 1-83 " " " " " " " OCH.sub.2
COO(cyclopentyl) 1-84 " " " " " " " OCH.sub.2 -(1-pyrazolyl) 1-85 " " "
" " " " 4-[C.sub.2 H.sub.5 OOCCH(CH.sub.3)O]-phenoxy 1-86 " " " " " " "
OCH.sub.2 -(2-thienyl) 1-87 " " " " " " " OCH(CH.sub.3)-(3-CH.sub.3
-1,2,4-oxadiazol-5-yl) 1-88 4-Cl-phenyl (CH.sub.2).sub.4 " " " Cl "
OCH(CH.sub.3).sub.2 1-89 " " " " " H " " 1-90 " (CH.sub.2).sub.2
CH(F)CH.sub.2 " " " F CH.sub.3 " 1-91 " " " " " " CN " 1-92 " " " " " "
CN OCH.sub.2 CCH 1-93 " (CH.sub.2).sub.4 " " " " Cl SCH(CH.sub.3).sub.2
1-94 " " " " " " " SCH.sub.2 CCH 1-95 " " " " " " " SCH.sub.2
COOCH.sub.2 CH.sub.3 1-96 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl
SCH(CH.sub.3)COOCH.sub.2 CH.sub.3 1-97 " " " " " " " SCH.sub.2 -phenyl
1-98 " " " " " " " S-(tetrahydro-2-pyranyl) 1-99 " " " " " " " NHCH.sub.2
COOCH.sub.2 CH.sub.3 1-100 " " " " " " " N(CH.sub.3).sub.2 1-101 " " "
" " " " NCH.sub.3COOCH.sub.2
CH.sub.3 1-102 " " " " " " " NHCOCH(CH.sub.3)CH.sub.2 CH.sub.3 1-103 "
" " " " " " NHCH(C.sub.2 H.sub.5)P(O)(C.sub.2 H.sub.5)(OC.sub.2 H.sub.5)
1-104 CH.sub.2CHCH.sub.3 " " " " " " SCH(CH.sub.3).sub.2 1-105 4-Cl-pheny
l " " " " " " COOCH(CH.sub.3).sub.2 1-106 " (CH.sub.2).sub.2
CH(F)CH.sub.2 " " " " " " 1-107 " (CH.sub.2).sub.2 CF.sub.2 CH.sub.2 "
" " " " " 1-108 " " " " " " " COOCH(CH.sub.2F).sub.2 1-109 " " " " " " "
COOCH.sub.2 CH.sub.2 OCH.sub.3 1-110 " " " " " " " COONC(CH.sub.3).sub.2
1-111 " " " " " " " COOCH.sub.2 CH.sub.2 -F 1-112 " (CH.sub.2).sub.4 " "
" " " COOCH.sub.2 CH.sub.2 OSi(CH.sub.3).sub.3 1-113 4-Cl-phenyl
(CH.sub.2).sub.4 O O O F Cl COOCH.sub.2 COOSi(CH.sub.3).sub.3 1-114 " "
" " " " " COOCH.sub.2
Si(CH.sub.3).sub.3 1-115 " " " " " " " COOCHCH.sub.3CH.sub.2
Si(CH.sub.3).sub.3 1-116 " " " " " " " COOCH.sub.2 CH.sub.2
PO(OCH.sub.3).sub.2 1-117 " " " " " " " COOCH(CH.sub.2
CH.sub.3)PO(OCH.sub.3).sub.2 1-118 " " " " " " " COOCH.sub.2
COOCH.sub.2 CH.sub.3 1-119 " " " " " " " COOCH.sub.2 OCOCH.sub.3 1-120
" " " " " " " COOCH(CH.sub.3)OCO-piperidin-1-yl 1-121 " " " " " " "
CON(CH.sub.3).sub.2 1-122 " " " " " " " CONCH.sub.3OCH.sub.3 1-123 " " "
" " " " CONHSO.sub.2 CH.sub.3 1-124 " " " " " " " CONHOCH.sub.2 COOEt
1-125 " " " " " " " CONHCH.sub.2 COOEt 1-126 " " " " " " " CN 1-127 " "
" " " " " CHO 1-128 " " " " " " " COCH.sub.3 1-129 " " " " " " "
4-COOC.sub.2 H.sub.5
-1,3-dioxolan-2-yl 1-130 4-Cl-phenyl (CH.sub.2).sub.4 O O O F Cl
2-CH.sub.3
-1,3-dioxolan-2-yl 1-131 " " " " " " " 4,4-di(CH.sub.3)-4,5-dihydro-
1,3-oxazol-2-yl 1-132 " " " " " F CN COOCHCH.sub.3CH.sub.2 CH.sub.3
1-133 " " " " " F Cl CH.sub.3 1-134 " " " " " " " CH.sub.2
CH(CH.sub.3).sub.2 1-135 " " " " " " " CH.sub.2 COOCH.sub.2 CH.sub.3
1-136 " " " " " " " CH.sub.2 C(CN)(CH.sub.3)COOC.sub.2 H.sub.5 1-137 " "
" " " " " CH.sub.2 C(CH.sub.3)(COOC.sub.2 H.sub.5).sub.2 1-138 " " " " "
" " CH.sub. 2 OCH.sub.3 1-139 " " " " " " " CH.sub.2 OCH.sub.2 COOEt
1-140 " " " " " " " CH.sub.2 NHCH.sub.2 COOEt 1-141 " " " " " "
CH.sub.2 CH.sub.2 CN 1-142 " " " " " " " CH.sub.2 CH.sub.2 COOCH.sub.3
1-143 " " " " " " " CH.sub.2 CH(CH.sub.3)COOEt 1-144 " " " " " " "
CHCHCN 1-145 " " " " " " " CHCHCOOCH.sub.3 1-146 4-Cl-phenyl (CH.sub.2).s
ub.4 O O O F Cl CHCBrCOOCH.sub.3 1-147 " (CH.sub.2).sub.2 CH(F)CH.sub.2
" " " " " CHCHCOOCH.sub.3 1-148" " " " " " " CHC(CH.sub.3 )CH.sub.2
COOCH.sub.3 1-149 " (CH.sub.2).sub.4 " " " " " CH.sub.2 SCH.sub.3 1-150
" " " " " " " CH.sub.2 CO.sub.2
CH.sub.3 1-151 4-CN-phenyl (CH.sub.2).sub.2 CH(F)CH.sub.2 " " " " "
OCH(CH.sub.3).sub.2 1-152 4-CH.sub.3 SO.sub.2 -phenyl " " " " " " "
1-153 4-CF.sub.3 -phenyl " " " " " " " 1-154 3,4-Cl.sub.2 -phenyl " " "
" " " " 1-155 4-(CH.sub.3).sub.2 NSO.sub.2 -phenyl " " " " " " " 1-156
4-F-phenyl " " " " " " " 1-157 (CH.sub.3).sub.2 NCO-phenyl " " " " " " "
1-158 1-cyclohexenyl " " " " " " " 1-159 (CH.sub.2).sub.4N " " " " " "
" 1-160 (CH.sub.2).sub.5N " " " " " " " 1-161 4-Cl-phenyl CH.sub.2
CH(F)CH(F)CH.sub.2 " " " " " " 1-162 " " " " " " " OCH.sub.3 1-163
4-Cl-phenyl CH.sub.2 CH(F)CH(F)CH.sub.2 O O O F Cl OCHCH.sub.3 CCH 1-164
" " " " " " " OCH.sub.2
CCH 1-165 CHCHCH.sub.2 " " " " " " OCH(CH.sub.3).sub.2 1-166 CH.sub.2CH
" " " " " " " 1-167 4-CH.sub.3 OCO-phenyl CH.sub.2 CH(F)(CH.sub.2).sub.2
" " " " " " 1-168 Cl.sub.3 CCHCl " " " " " " " 1-169 CH.sub.2CCH.sub.3 "
" " " " " " 1-170 CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 (CH.sub.2).sub.4 "
" " " " " 1-171 CH.sub.2 CCl.sub.3 " " " " " " " 1-172 Cl.sub.3
CC(CH.sub.3).sub.2 " " " " " " OCH(CH.sub.3).sub.2 1-173 ClCH.sub.2
CH.sub.2 " " " " " " " 1-174 4-Cl-phenyl CH.sub.2 CF.sub.2
(CF.sub.2).sub.2 " " " " " " 1-175 " CHCHSCH.sub.2 " " " " " " 1-176 "
(CH.sub.2).sub.2 CH(F) " " " " " 1-177 " (CH.sub. 2).sub.2 OCH.sub.2 " "
" " " " 1-178 " (CH.sub.2).sub.2 N(CH.sub.3)CH.sub.2 " " " " " " 1-179 " C
H.sub.2 CFCHCH.sub.2 " " " " " OCH.sub.2 CCH 1-180 " " " " " " "
OCH.sub.3 1-181 4-Cl-phenyl CH.sub.2
CFCHCH.sub.2 O O O Cl Cl OCH(CH.sub.3).sub.2 1-182 " CH.sub.2
CHCFCH.sub.2 " " " " " " 1-183 phenyl CH.sub.2 CFCFCH.sub.2 " " " " " "
1-184 CH.sub.2CH " " " " " " " 1-221 phenyl (CH.sub.2).sub.2 CHFCH.sub.2
" " " F Br " 1-222 " " " " " " " COOCH(CH.sub.3).sub.2 1-223 " " " " " "
CN OCH(CH.sub.3).sub.2 1-224 " " " " " " " COOCH(CH.sub.3).sub.2 1-225 "
" " " " " CH.sub.3 OCH(CH.sub.3).sub.2 1-226 " " " " " " " COOCH(CH.sub.3
).sub.2 1-227 " " " " " " Cl CH(CH.sub.3).sub.2
Compd. R.sub.1 A X Y Z Ar
1-185 4-Cl-phenyl (CH.sub.2).sub.4 O O O 1-(2-propinyl)-5-F-benzo[d]pyr
azol-6-yl 1-186 " " " " " 4-CH.sub.3 -7-F-benzo[e]-1,3-dioxine-6-yl
1-187 " " " " " 2,2,5-tri-F-benzo[d]dioxole-6-yl 1-188 " " " " "
6-F-2,3-dihydro-benzo[b]-1,4-dioxin-7-yl 1-189 " " " " " 4-(2-propinyl)-7
-F-benzo[b]-1,4-thiazin-3-on-6-yl 1-190 " (CH.sub.2).sub.2 CH(F)CH.sub.
2 " " " 4-(2-propinyl)-7-F-Ar.sub.1 1-191 " (CH.sub.2).sub.4 " " "
4-allyl-7-F-Ar.sub.1 1-192 " (CH.sub.2).sub.2 CH(F)CH.sub.2 " " "
4-CH.sub.3 -7-F-Ar.sub.1 1-193 " (CH.sub.2).sub.4 " " " 4-(C.sub.2
H.sub.5 OOCCH.sub.2)-7-F-Ar.sub.1 1-194 " " " " " 4-(CH.sub.2
OCH.sub.2)-7-F-Ar.sub.1 1-195 " " " " " 4-(CNCH.sub.2)-7-F-Ar.sub.1
1-196 " " " " " 4-CH.sub.2 -(tetrahydropyran-4-yl)-7-F-Ar.sub.1 1-197 "
" " " " 4-CH.sub.2 -(5,6-dihydro-2H-thiin-3-yl)-7-F-Ar.sub.1 1-198 " " "
" " 4-CH.sub.2
(2-pyridyl)-7-F-Ar.sub.1 1-199 " " " " " 4-(pyrazin-2-yl-methyl)-7-F-Ar.
sub.1 1-200 " " " " " 4-(1,2-oxazole-3-yl-methyl)-7-F-Ar.sub.1 1-201 " "
" " " 4-(5-CH.sub.3 -1,2,4-oxdiazol-3-yl-methyl)-7-F-Ar.sub.1 1-202
4-Cl-phenyl (CH.sub.2).sub.4 O O O 1-(2-propinyl-6-F-Ar.sub.2 1-203 " "
" " " 1-allyl-6-F-Ar.sub.2 1-204 " (CH).sub.2
CHFCH.sub.2 " " " 1-(2-propinyl)-6-F-Ar.sub.3 1-205 " " " " " 1-allyl-6-
F-Ar.sub.3 1-206 " " " " " 1-allyl-6-F-quinoline-2(1H)-on-7-yl 1-207 " "
" " " 3-(2-propinyl)-6-F-benzo[d]-1,3-oxazole-2(3H)-on-5-yl 1-208 "
(CH.sub.2).sub.4 " " " 3-(2-pyridyl-CH.sub.2)-6-F-Ar.sub.4 1-209 " " " "
" 3-(1,2-oxazole-3-yl-CH.sub.2)-6-F-Ar.sub.4 1-210 " " " " " 5-F-1-CH.sub
.3
indol-6-yl 1-211 " " " " " 6-F-chroman-7-yl 1-212 " " " " " 5-F-2,3-dihy
drobenzo[b]furan-6-yl 1-213 " " " " " 5-F-indan-1-on-6-yl 1-214 " " " "
" 7-F-4-isopropyl-chromen-2-on-6-yl 1-215 " " " " " 5-F-1-(2-propinyl)-1-
H-indol-2,3-dion-6-yl 1-216 " " " " " 5-F-benzo[d]imidazol-2(1H,3H)-on-6-
yl 1-217 " " " " " 5-F-1,3-di(CH.sub.3)-1,3-dihydro-indol-2-on-6-yl
1-218 " " " " " 1-allyl-5-F-1,3-dihydro-indol-2-on-6-yl 1-219 " (CH.sub.2
).sub.2
CHFCH.sub.2 " " " 6-F-1(2-propinyl)-3,4-dihydroquinolin-2(1H)-on-7-yl
1-220 " " " " " 1-(2-propinyl)-5-F-benzo[d]-1,2,3-triazol-6-yl
Key to Abbreviations
(1) isomeric mixture of 4- and 5-substituted compound
(2) Ar=2-R.sub.2 -4-R.sub.3 -5-R.sub.4 -phenyl
(3) Ar.sub.1 =2-R.sub.2 -4-dihydro-benzo[b]-1,4-oxazin-3-on-6-yl
(4) Ar.sub.2 =3,4-dihydro-2H-quinoxalin-2-on-7-yl
(5) Ar.sub.3 =1 H-quinoxalin-2-on-7-yl
(6) Ar.sub.4 Benzo[d]-1,3-thiazol-2(3H)-on-5-yl
(7) numbering convention
##STR9##
EXAMPLE 2-1
3[[(4-chloro-2-fluoro-5-isopropoxyphenyl)aminojcarbonyl-4-thiomorpholine
carboxylic acid phenyl ester-1,1 dioxide
To 2.25 g (0.005 mol) of
3[[(4-chloro-2-fluoro-5-isopropoxyphenyl)-aminolcarbonyl-4-thiomorpholinec
arboxylic acid-phenyl ester in 20 ml of methylene chloride (CH.sub.2
CH.sub.2) is added dropwise, without cooling a dried (Na.sub.2 SO.sub.4)
solution of 4 g of m-chloro-perbenzoic acid (55%/.about.0.013 mol) in 200
ml of CH.sub.2 CH.sub.2. After the exothermic (28.degree.) reaction has
subsided, the reaction solution is stirred 16 hours longer at ambient
temperature and is then washed with 140 ml of water, which contains 14 g
of KHCO.sub.3 and 2 g of NaHSO.sub.3. Then the organic layer is separated,
washed with water (150 ml), dried (Na.sub.2 SO.sub.4) and evaporated in
vacuo. The residue is chromatographed on a silica gel column.
Elution with ethyl acetate affords the title compound, which is homogenous
by TLC (Rf=0.31 on silica gel with ethyl acetate-hexane 1:1).
In an analogous manner, the folloving compounds of formula (I) set forth in
Table 2 are made.
TABLE 2
__________________________________________________________________________
##STR10##
Compd.
R.sub.1
A X Y Z R.sub.2
R.sub.3
R.sub.4 m.p. or R.sub.f on silica
__________________________________________________________________________
gel
2-2 phenyl
(CH.sub.2).sub.2 SO.sub.2 CH.sub.2
O O O F Cl
OCH.sub.3 74-76.degree.
2-3 " " " " " " " OCH.sub.2 CH.sub.3
0,35 (ethyl acetate-hexane 1:1)
2-4 " " " " " " " OCH.sub.2 CH.sub.2 CH.sub.3
0.35 (ethyl acetate-hexane 1:1)
2-5 " " " " " " " OC.sub.4 H.sub.9 -sec.
0,38 (ethyl acetate-hexane 1:1)
2-6 " " " " " " " OC.sub. 5 H.sub.9 -cycl.
0,37 (ethyl acetate-hexane 1:1)
2-7 " " " " " " " OCH.sub.2 CCH
129-131.degree.
2-8 " " " " " " " OCH(CH.sub.3)CCH
0,58 (ethyl acetate)
2-9 CH.sub.3
" " " " " " OCH(CH.sub.3).sub.2
168-169.degree.
2-10 " " " " " " " OCH(CH.sub.3)CCH
R.sub.f = 0,47 (ethyl
__________________________________________________________________________
acetate)
EXAMPLE 3-1
3[[(4-Chloro-2-fluoro-5-isopropoxyphenyl)azinolearbonyl]-4-thio morpholine
carboxylic acid methyl ester-1-oxide
To 13,3 g (0,034 mol) of
3[[(4-chloro-2-fluoro-5-isopropoxyphenyl)amino]carbonyl]-4-thiomorpholinec
arboxylic acid-methyl ester in 150 ml of dry methylene chloride is added
dropwise with stirring the dried (Na.sub.2 SO.sub.4) solution of 7,25 g
m-chloroperbenzoic acid (80 %; 0,034 mol) at such a rate, that the
temperature does not rise above 5.degree.. After being kept at 50 for 20
hours, the reaction solution is washed with 500 ml of water which contains
50 g of NaHCO.sub.3 and 5 g of NaHSO.sub.3.
Then the organic layer is separated, washed with water (250 ml), dried
(Na.sub.2 SO.sub.4) and evaporated in vacuo.
The residue is chromatographed on a silica gel column.
Elution with ethyl acetate affords the title compound as a reddish
amorphous solid which is homogeneous by TLC (Rf=0,07 on silica gel with
ethyl acetate).
In an analogous manner, the following compounds set forth in Table 3 are
made.
TABLE 3
__________________________________________________________________________
##STR11##
Compd.
No. R.sub.1
A X Y Z R.sub.2
R.sub.3
R.sub.4 m.p. or Rf on silica
__________________________________________________________________________
gel
3-2 phenyl
(CH.sub.2).sub.2 SOCH.sub.2
O O O F Cl
OCH(CH.sub.3).sub.2
152-154.degree.
3-3 " " " " " " " OCH.sub.2 CCH
113-115.degree.
3-4 " " " " " " " OCH(CH.sub.3)CCH
R.sub.f = 0.13 (ethylacetate)
3-5 CH.sub.3
" " " " " " OCH(CH.sub.3).sub.2
R.sub.f = 0.08
__________________________________________________________________________
(ethylacetate)
INTERMEDIATES
EXAMPLE 4-1
Pipecolic acid 4-chloro-2-fluoro-5-isopropoxy anilide
To a suspension of 18.4 g (0.1 mol) pipecolic acid chloride hydrochloride
in 400 ml methylenechloride are added 20.3 g (0.1 mol)
4-chloro-2-fluoro-5-isopropoxy aniline. After the exothermic (30.degree.
C.) reaction has subsided, 18 g NaHCO3 are added and the reaction mixture
is stirred for 30 minutes at room temperature. 30 ml of water is added and
stirring is continued for 1 hour. After the addition of 200 ml water the
organic phase is separated, washed with 100 ml water, dried (MgSO.sub.4)
and evaporated in vacuo. After treatment of the residue with pentane the
compound is obtained in form of white crystals. Mp. 960.degree. C.
In an analogous manner, the following compounds of formula (II) set forth
in Table 4 are made.
TABLE 4
__________________________________________________________________________
##STR12##
Compound
##STR13## R.sub.2
R.sub.3
R.sub.4
mp or R.sub.f
__________________________________________________________________________
4-2 piperid-2-yl
F Cl H 88.degree. C.
4-3 " " " OCH.sub.2 CH.sub.3
88.degree. C.
4-4 " " " OH.sub.2 CH.sub.2 CH.sub.3
89.degree. C.
4-5 " " " OCH.sub.3
142.degree. C.
4-6 " " " OCH(CH.sub.3).sub.2
94.degree. C.
4-7 " " " OCHCOOEt
R.sub.f = 0,1(Ether)
CH.sub.3
4-8 " " " OCOOCH.sub.3
126.degree. C.
4-9 " H " COOCH.sub.2 CH.sub.3
109.degree. C.
4-10 1,2,3,6-tetrahydro-
F " OCH(CH.sub.3).sub.2
71.degree. C.
pyridin-2-yl
4-11 1,4-thiomorpho-
" " " 84.degree. C.
lin-3-yl
4-12 2,3-dehydro-1,4-
" " "
thiomorpholin-3-yl
4-13 3-F-piperidin-2-yl
F Cl OCH(CH.sub.3).sub.2
4-14 4-F-piperidin-2-yl
" " "
4-15 5-F-piperidin-2-yl
" " "
4-16 4,4-di-F-piperidin-2-yl
" " "
4-17 5,5-di-F-piperidin-2-yl
" " "
4-18 4-F-1,2,3,6-tetrahydro-
" " "
pyridin-2-yl
4-19 5-F-1,2,3,6-tetrahydro-
" " "
pyridin-2-yl
4-20 4,5-di-F-1,2,3,6-
F Cl OCH(CH.sub.3).sub.2
tetrahydro-pyridin-2-yl
4-21 4,5-di-F-piperidin-2-yl
" " "
4-22 3,3-di-F-piperidin-2-yl
" " "
__________________________________________________________________________
Biology
The herbicidal activity of the compounds of this application is
demonstrated by experiments carried out for the pre-emergence and
post-emergence control of a variety of weeds. Such weeds include Abutilon
theophrasti, Amaranthus retroflux, Sinapis alba, Solanum nigrum, Bromus
tectorum, Setaria viridis, Avena fatua, and Echinochloa crus-galli.
In preemergence testing, small plastic greenhouse pots filled with dry soil
are seeded with the various weed seeds. Twenty-four hours or less after
the seeding, the pots are sprayed with water until the soil is wet and the
test compounds formulated as aqueous emulsions of acetone solutions
containing emulsifiers are sprayed at the indicated concentrations
emulsifiers are sprayed on the surface of the soil. After spraying, the
soil containers are placed in the greenhouse and provided with
supplementary heat as required and daily or more frequent watering. The
plants are maintained under these conditions for a period of from 14 to 21
days, at which time the conditions of the plants and the degree of injury
to the plants is rated.
In post-emergence testing, the compounds to be tested are formulated as
aqueous emulsions and sprayed on the foliage of the various weed species
that have attained a prescribed size. After spraying, the plants are
placed in a greenhouse and watered daily or more frequently. Water is not
applied to the foliage of the treated plants. The severity of the injury
is determined 21 days after treatment and is rated.
In general, the compounds of this application demonstrate good activity
against most of the weed varieties noted above. They are particularly
active against Abutilon theophrasti and Solanum nigrum, in both pre- and
post-emergence testing.
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